Molecular Transport Junctions: Current from Electronic Excitations in the Leads

Michael Galperin,
1
Abraham Nitzan,
2
and Mark A. Ratner
1
1
Department of Chemistry and Nanotechnology Center, Northwestern University, Evanston, Illinois 60208, USA
2
School of Chemistry, The Sackler Faculty of Science, Tel Aviv University, Tel Aviv 69978, Israel
(Received 17 November 2005; published 25 April 2006)
Using a model comprising a two-level bridge connecting free electron reservoirs we show that coupling
of a molecular bridge to electron-hole excitations in the leads can markedly effect the source-drain current
through a molecular junction. In some cases, e.g., molecules that exhibit strong charge transfer transitions,
the contribution from electron-hole excitations can exceed the Landauer elastic current and dominate the
observed conduction.
DOI: 10.1103/PhysRevLett.96.166803 PACS numbers: 73.23.b, 73.50.Lw, 85.65.+h, 85.80.b
Introduction. Electron transport in molecular tunnel
junctions has been the focus of intense recent research
[14]. Theoretical modeling of tunnel conduction [5,6]
starts from Hamiltonians that contain electron transfer
(tunneling) interactions between molecule and leads as
essential elements for current transport in such junctions.
At the same time, energy-transfer interactionsexcitation
(deexcitation) of the molecule accompanied by electron-
hole pair annihilation (creation) in the metal are known
to strongly affect the lifetime of excited molecules near
metal surfaces [7]. An essential difference between these
interactions is that electron transfer is a tunneling process
that depends exponentially on the molecule-metal dis-
tance, while energy transfer is associated with dipolar
coupling that scales like the inverse cube of this distance,
and can therefore dominate at larger distances.
How will such dipolar interactions affect the conduction
properties of molecular junctions? Here we address this
question by using the nonequilibrium Green function
(NEGF) formalism to derive an expression for the conduc-
tion in a junction model that contains both electron and
energy-transfer interactions, then analyze several examples
with reasonable parameters. We conclude that current
caused by electron-hole excitations in the leads may be
signicant, sometimes even dominant, in situations when
strong asymmetry in the molecule-lead coupling, of a
particular type explained below, is present.
As an extreme example consider the case where the
highest occupied molecular orbital (HOMO) is coupled
only to one lead, while the lowest unoccupied molecular
orbital (LUMO) is coupled only to the other. Such a
junction cannot pass current (in the absence of electronic
correlations) if the dipolar interaction is absent. However,
mixing of the HOMO and LUMO orbitals by dipolar
coupling to the leads makes conduction possible.
Realistic situations will not be that extreme; still, whenever
the HOMO-LUMO transition is associated with electronic
charge transfer along the molecular bridge, we expect
some degree of such asymmetry. For example, the dipole
moment of DMEANS (4-Dimethylamino-4-nitrostilbene)
is 7 D in the ground state and 31 D in the rst excited
singlet state [8], and 40 A

CdSe nanocrystals change their

dipole from 0 to 32 D upon transition from their ground to
the rst excited state [9]. We have recently shown [10] that
such situations may give rise to light induced current under
zero voltage. We show below that another manifestation of
this charge transfer property is the increasing importance
of dipolar energy-transfer interactions between molecule
and leads in determining the junction conduction
properties.
Model and method. We consider a tunneling junction
(Fig. 1) consisting of a molecule positioned between two
metal contacts (L and R). The molecule is represented by
its HOMO, }1), and LUMO, }2), with energies "
1
and "
2
and gap "
21
"
2
"
1
. The contacts are assumed to be
free electron reservoirs, each at its own equilibrium, char-
acterized by electronic chemical potentials
L
and
R
,
where the difference
L

R
e is the imposed volt-
age. The corresponding Hamiltonian is
^
H
^
H
0
+
^
V
M
+
^
V
N
; (1)
FIG. 1. The junction model. The dark and light gray areas
denote occupied and unoccupied leads states that are connected
via the molecular bridge. The latter is represented by its
HOMO (1) and LUMO (2) levels. The solid-line double arrows
represent the electron transfer interactions, the dashed double
arrows, the energy-transfer interactions, and the vertical open
arrows, the electron excitation/deexcitation processes in the
molecule and the metals (see text for notations).
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0031-9007=06=96(16)=166803(4)$23.00 166803-1 2006 The American Physical Society
^
H
0

X
m1;2
"
m
^ c
|
m
^ c
m
+
X
kL;R
"
k
^ c
|
k
^ c
k
; (2)
^
V
M

X
KL;R
X
m1;2;kK
(V
(MK)
km
^ c
|
k
^ c
m
+H:c:); (3)
^
V
N

X
KL;R
X
kk
/
K
(V
(NK)
kk
/
^ c
|
k
^ c
k
/ ^ c
|
2
^ c
1
+H:c:); (4)
where H.c. denotes the Hermitian conjugate. Here the
operators ^ c
m
and ^ c
|
m
(m 1; 2) are annihilation and crea-
tion operators of electrons in the bridge, while ^ c
k
and ^ c
|
k
are annihilation and creation operators of electrons in the
leads. The Hamiltonian
^
H
0
is a sum of terms that corre-
spond to the isolated molecule (represented by its HOMO-
LUMO levels in our model) and free electron reservoirs
representing the leads.
^
V
M
describes the electron transfer
(tunneling) process between these subsystems.
^
H
0
+
^
V
M
is
the standard Hamiltonian used in simple models of mo-
lecular conduction that yield the Landauer conduction
expression [Eq. (11) below]. The additional term
^
V
N
rep-
resents coupling of the molecular HOMO-LUMO transi-
tion to electron-hole excitations in the leads which is often
used in models of energy transfer between the molecule
and the metals. The effect of this interaction on the junction
transport properties is the subject of our discussion. Effects
of electron-hole recombination on the bridge were previ-
ously considered [11] at the level of master equation
approach to transport.
In the Keldysh NEGF formalism [12] the steady-state
current through the junction is given in terms of the lesser
and greater Green functions (GFs), G
(;)
, and the corre-
sponding self-energies (SEs) associated with the electron
transfer process,
<;>
MK
, by [13]
I
sd

e
@
Z
dE
2
Trj
<
MK
(E)G
>
(E)
>
MK
(E)G
<
(E)|
(5)
calculated at the left (K L with + sign) or right (K
R with sign) contact, where the direction from left to
right is chosen to be positive. The GFs G
(;)
needed in (5)
can be obtained from the Keldysh equation
G
(;)
(E) G
r
(E)
(;)
(E)G
a
(E) (6)
where the retarded and advanced GFs, G
r;a
, are given by
the Dyson equation
G
r
(E) jE H
m
0

r
(E)|
1
; G
a
(E) jG
r
(E)|
|
:
(7)
Here H
m
0
is a matrix that corresponds to the molecular part
(rst term on the right) of the Hamiltonian (2) and
r
(E) is
the retarded self-energy matrix due to both e transfer and
dipolar coupling to the leads. These are 2 2 matrices in
the representation of molecular states }1) and }2).
The SEs needed in Eqs. (5)(7) are obtained within the
usual diagrammatic technique on the Keldysh contour. In
the noncrossing approximation [14] they contain additive
contributions associated with the electron and energy-
transfer processes at the two leads (L and R):

(ML)
+
(MR)
+
(NL)
+
(NR)
: (8)
The evaluation of these self-energies and their corre-
sponding retarded, advanced, lesser, and greater projec-
tions on the real time axis is described in detail in Ref. [15].
The additive structure [Eq. (8)] translates into additive
expressions for the corresponding projections and makes
it possible to separate the lesser and greater Green func-
tions [Eq. (6)], and consequently also the source-drain
current [Eq. (5)], into contributions due to direct electron
transfer to the leads, I
et
sd
, and coupling to the electron-hole
excitations, I
eh
sd
.
I
sd
I
et
sd
+I
eh
sd
: (9)
In particular, the self-energies associated with the electron
transfer processes are obtained in the wide band approxi-
mation in the familiar forms [16,17]

(MK)r
mm
/
j
(MK)a
m
/
m
|

i
mm
/
(MK)
m
=2; (10a)

(MK)<
mm
/
i
mm
/ f
K
(E)
(MK)
m
; (10b)

(MK)>
mm
/
i
mm
/ j1 f
K
(E)|
(MK)
m
; (10c)

(MK)
m
2
X
kK
}V
(MK)
km
}
2
(E "
k
); (10d)
f
K
(E) jexp(E
K
)=k
B
T +1|
1
(10e)
(note that the matrix
(MK)
was assumed diagonal, disre-
garding possible level mixing due to coupling to the leads),
where
K
, K L; R, are the chemical potentials of the left
and right leads, respectively. This results in the standard
Landauer expression for I
et
sd
:
I
et
sd

e
@
Z
+

dE
2

X
m1;2

(ML)
m
G
r
mm
(E)
(MR)
m
G
a
mm
(E)jf
L
(E) f
R
(E)|
(11)
The evaluation of I
eh
sd
is more involved. The SEs asso-
ciated with the energy-transfer processes can be expressed
in terms of the GFs [see Eqs. (19), (22), and (36) of
Ref. [15] ], and the self-consistent solutions of the resulting
coupled equations are found by iterations. We use the level
populations, n
m
i
R
dE
2
G
<
mm
(E) (m 1; 2), as a test for
convergence, which is declared when the population values
at subsequent iteration steps do not change within a pre-
dened tolerance, chosen below as 10
6
.
The results shown in Figs. 2 and 3 were obtained from
this procedure. A simple analytical expression for I
eh
sd
can
be obtained when
m

(L)
m
+
(R)
m
< "
21
(where
K
m

(MK)
m
+
(NK)
m
with
(NK)
m
2 Im
(NK)r
mm
) [18] and in the
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strong bias limit. Strong bias implies, e.g., for nega-
tively biased left electrode, that
L
> "
2
and
R
< "
1
so
that f
L
1 and f
R
0 in the relevant energy range.
Under these conditions the results for the Landauer current
I
et
sd
and for the electron-hole excitations induced current I
eh
sd
are obtained [15] in the forms
I
et
sd

e
@
X
m1;2

(ML)
m

(MR)
m

m
sgn(
L

R
); (12)
I
eh
sd

e
@
B

(ML)
2

(MR)
1

2
(
L

R
)

(ML)
1

(MR)
2

2
(
R

L
)

; (13)
where (x) 1 for x >0 and 0 for x <0, and where B
B
(L)
+B
(R)
is the function
B
(K)
(!;
K
) 2
Z
dE
X
kk
/
K
}V
(NK)
kk
/
}
2
(E "
k
)
(E +! "
k
/ )f
K
(E)j1 f
K
(E +!)|
2}V
(NK)
}
2

eh
K
(!) (14)
evaluated at ! "
2
"
1
. Here
eh
K
(!) is density of
electron-hole excitations in the lead K. Equations (12)
and (13) show that the magnitude of I
et
sd
depends on the
product
(ML)
m

(MR)
m
(m 1; 2), while I
eh
sd
is determined by
the mixed products
(ML)
2

(MR)
1
or
(ML)
1

(MR)
2
. The relative
contribution of the latter current component will be sig-
nicant in asymmetric coupling situations, e.g., for
L
>

R
when
(ML)
2
>
(MR)
2
and/or
(MR)
1
>
(ML)
1
. Note that,
since
(ML)
2

(MR)
1
can be different from
(ML)
1

(MR)
2
, }I
eh
sd
}
can be asymmetric to bias reversal (see also Fig. 2). Below
we compare the magnitude of the two contributions to the
current for different junction parameters.
Numerical results. In the calculations reported below
we used the following standard choice of parameters:
T 300 K, "
1
0 eV, "
2
2 eV, and
(M)
1

(M)
2

0:2 eV. Values of other parameters are indicated in the
gures. The Fermi energy is taken at the midpoint of the
HOMO-LUMO gap and the electrochemical potentials in
the left and right leads are assumed to shift with the voltage
bias symmetrically relative to this point. Numerical inte-
gration was done on the energy grid spanning range from
3 to 5 eV using integration step 10
3
eV.
Figure 2 depicts the current-voltage characteristic of the
junction for the cases of symmetric and asymmetric cou-
pling between the leads and the molecular LUMO. Shown
are the total current and its two components. The following
points are noteworthy: (1) In the symmetric case the cur-
rent is dominated by the usual electron and/or hole trans-
port through the LUMOand/or HOMO, respectively, and is
symmetric with respect to voltage reversal. (2) The asym-
metric case shows a signicant contribution of the current
associated with electron-hole excitations when the LUMO
is coupled more strongly to the negatively biased electrode.
Indeed, I
eh
sd
is expected to be pronounced when the LUMO
is populated and the HOMO is empty, which happens at
such bias. (3) The asymmetric LUMO coupling leads to
asymmetry in I
eh
sd
and consequently in the total current with
respect to bias reversal.
Figure 3 shows the results of a model study of the
dependence of the source-drain current on the molecule-
lead distance R. These results are obtained using
(MK)
m

A
(MK)
m
expj
(MK)
m
R|, which accounts for the tunneling
nature of electron transfer, and taking B
(K)

(K)
=R
3
,
which reects a dipolar distance dependence of the energy
transfer to the leads [7]. The parameters used are A
(ML)
1

A
(MR)
1
0:27 eV, A
(ML)
2
0:52 eV, A
(MR)
2
0:027 eV,

(MK)
m
1

A
1
, and
(K)
0:01 eVA
3
(K L; R and
m 1; 2). The choice of A
(MK)
m
corresponds to a total life-
time broadening for electron transfer into the electrodes of
0.2 eV at a distance (from each electrode) of 1 A

. The
choice of
(K)
corresponds to taking B
(K)
0:01 eVat this
distance. Both choices reect the orders of lifetimes ob-
-2
-1
0
1
( 10
-5
)
I
s
d
(
A
)
-6 -4 -2 0 2 4 6
e (eV)
-1
0
1
( 10
-5
)
I
s
d
(
A
)
(a)
(b)
FIG. 2 (color online). The source-drain current I
sd
vs applied
voltage . Shown are the total current I
sd
(solid red line) and its
components due to direct electron transfer I
et
sd
(dashed green line)
and electron-hole excitations I
eh
sd
(dotted blue line), for the sym-
metric
(ML)
1;2

(MR)
1;2
0:1 eV (a) and asymmetric
(ML=R)
1

0:1 eV,
(ML)
2
0:19 eV, and
(MR)
2
0:01 eV (b) cases.
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served for the corresponding processes for molecules ad-
sorbed on metal surfaces.
The results shown in Fig. 3 demonstrate an important
aspect of the distance dependence of the two contributions
to the total current. Obviously, both I
et
sd
and I
eh
sd
involve
electron transfer between molecule and leads, therefore
both drop exponentially with increasing tunneling length.
Their relative importance, however, depends on the details
of the molecule-leads couplings. It is easily seen from
Eqs. (12) and (13) that I
eh
sd
=I
et
sd
B=. For small and
intermediate distances, where is dominated by the elec-
tron tunneling process, this ratio increases with increasing
distances. (Note that this limiting behavior is obtained only
when both left and right molecule-metal couplings de-
crease together. Experimentally, one of these distances
can be controlled by moving a tip, while the other can be
changed by adding insulating layers between molecule and
substrate [19,20].) Detailed calculation shows that this
ratio can in fact become substantially larger than 1 at large
molecule-lead distances, as seen in Fig. 3. In this case the
current is dominated by the contribution associated with
the electron-hole excitation process.
Conclusion. We have studied, within a simple model,
the effect of dipolar energy-transfer interaction between
molecule and leads on molecular conduction. We found
that such interaction, which leads to electron-hole excita-
tions in the contacts, can affect the current-voltage char-
acteristic of the junction in a substantial way and cannot in
general be disregarded. The contribution of this interaction
can dominate the overall conduction for particular asym-
metric coupling where the molecular LUMO and/or
HOMO are coupled differently to different leads. In addi-
tion, because of the different dependence of electron and
energy transfer on the molecule-leads distance, the relative
importance of I
et
sd
and I
eh
sd
depends on this distance, and can,
in some cases, result in strong dominance of I
eh
sd
at large
molecule-lead separations.
We thank the NSF-NNI program, the DARPA MolApps
initiative, and the Durint/MURI program of the DOD for
support. A. N. thanks the Israel Science Foundation and the
U.S.-Israel Binational Science Foundation for support.
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[18] Explicit expressions for
(N)
m
are obtained in this limit in
terms of the level populations n
m
(m 1; 2) [see Eq. (37)
of Ref. [15] ], which in turn are obtained from the self-
consistent calculations.
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2 4 6 8 10 12 14
R (Angstrom)
10
-11
10
-10
10
-9
10
-8
10
-7
10
-6
10
-5
I
s
d
(
A
)
FIG. 3 (color online). The source-drain current I
sd
at voltage
3 V vs molecule-leads distance R. See text for the choice of
coupling parameters. Shown are the total current I
sd
(solid red
line) as well as its I
et
sd
(dashed green line) and I
eh
sd
(dotted blue
line) components.
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